Azo dyestuffs.



UNITED STATES PATENT OFFICE.

NEAR COLOGNE, GERMANYpASSIGNORS TQ SYNTHETIC PATENTS .CO., INC., OF NEW YORK, N. Y., ACORPOBATION OF NEW YORK. v

" AZO DYESTUFFS.

No Drawing.

To all 'u'lm'm it may concern Y Beit known that we, AUGUST BLANK, Ca n. Hn nn amnon, and JOIIANNES JANsnN,

doctors of philosophy, chemists, citizens of i fiber and yield, when developed with suitable developers, .c. g. beta-naphthol, fast green shades. v

The new products are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in-water. Upon reduction with stannous chlorid and hydrochloric acid .they are broken, up into an aromatic amino compound, a diamino compound, a meta-aminobenzo derivative, 6. g.

a ,meta-ami-nobenzenyl or a meta-aminobenzoyl derivative of the 2-am1no-5-naphthol-7-sulfon1c acid and a benzene derlvative.

The process for producing the new dyes consists 1, in combining diazotized: alphaor beta-naphthylamin or their sulfonic acids with a suitable middle component capable of being diazotized after combination, in rediazotizing the monoazo dyesthus obtained, combining them with a meta-aminobenzenyl derivative of the 2.5-amino-naph thol-7-sulfomc acid such as meta-am1noanrinoplmnol; 2, in combining diazotized: acidyl-para-dlam1ns or para-mtrannns, or

derivatives of sult'onic vacids of these com-' pounds'with a suitable middle component capableof being diazotized after combination, .1n rediazotizlng the monoazo dyesthus obtained, combining them with a meta-ami- Specification of Letters Patent.

Application filed Am-114, 1914. Serial No. 829,687.-

Patented Aug. 17, 1915.

nobenzenyl derivative of the 2.5-amin0naphthol-7-sulfonic acid, such as meta-amino benzenyl 1.2 naphthylenedia-Inin 5- oxy-7- sulfonic acid or meta-aminobenzenyl-l thio- 2-amino-na hthylene-fi-oxy l-sulfonic acid,

in diazotizmg the products thus obtained, coupling them with resorcin or meta-aminophenol, and finally (according to the character of the amin initiall used) in either eliminating the acidyl ra ical or in reducing the nitro group; 3, in either further diazotizing the dyes obtained according. to No. 2 and coupling them after diazotation wit-h resorcin or meta-aminophenol,,or (according to thecharacter ofthe 'amin initially used in the process of 2) in either eliminating the acidyl radical from the acidyl compounds or reducing t e nitro group in the products obtained according to No. 2 prior to the final diazotation and combination, in tetrazotizing the aminoazo dyestuffs thus obtained and in coupling them with 2 molecules of resorcin or meta-aminophenol or with one molecule of meta-aminophenol and one molecule of resorcin.

Examples of the initial diazotizable com- 1-amino-2-naphtholethylether, cresidin, al-

pha naphthylamin, 1 amino 5 naphthol. Examples of the third components are: meta aminobenzoyl L 2 amino-5-naphthol-7- sulfonic acid, meta-aminobenzenyl-l.2-naphthylenediamin-5-oxy-7-sulfonic acid, metaaminophenyl 1.2 naphthothiazole 5-0xy-7- sulfonic acid.

In order to illustrate the new process more fully the following examples aregiven, the parts being by weight; v

- Example 1: 26 parts of xalyl-para-phenylenediamin sulfonic acid are dissolved in 300 parts of hot water withthe aid of sodium carbonate, the solution is cooled with ice to 55 0., acidulated with 35 parts of hydrochloric acid (spec. grav. 1.19) and diazotized with 6.9 parts of sodium nitrite.

The diazo compound is then added to a solution of 22.3 parts of 1-amino-2-naphtholcthylether (hydrochlorid) in500 parts of water and to the mixture which has to be stirred a solution of sodium acetate is slowly added until the copulation is complete. The ammoazodyestuii is filtered oil and 1s Y then dissolved in 500 parts of water with 10 the aid of sodium carbonate, cooled u'ith ice to C. and diazotized with 6.9 parts of sodium nitrite and 40 parts of hydro chloric acid. The mixture is stirred until the nitrous acid has disappeared and the diazo compound thus obtained is added to a solution of 35.5 parts of meta-aminobenze'nyl 1.2 naphthylenediamin 5 oxy-7-sulfonic acid of the formula:

- NLFQ in 1000 parts of water and 35 parts of sodium carbonate. After six hours the dye- OCgHg Instead of oxalyl-para-phenylenediamin sulfon-ic acid other acidyl-diamins or their sulfonic acids can be used. Instead of '1 'amino-2-naphtholethylether another suitcomplete. The dyestuff isfilteredofi', dissolved in water and sodium carbonate and diazotized with 6.9 parts of sodium nitrite and 40 parts of hydrochloric acid. When the nitrite has disappeared, the diazo' compound is added to a solution containing 37.2

parts of meta-aminobenzenyl1-thi0-2 aminoformula:

[stuff is salted out, dissolved in water and di'azotized with 6.9 parts of sodium nitrite and 50 parts or hydrochloric acid. When the nitrous acid has disappeared, the diazo compound is addedito-a solution of 11 parts of resorcin in 500 parts of water and 40 parts of sodium carbonate at a temperature of from 0 to 5 C. Subsequently it is slowly heated to boiling, 150 parts of soda lye per cent.) are added to it and it is boiled for half an hour. Then the soda lye is neutralized with hydrochloric acid, the dyestufi' is salted out. pressed and dried. It yields on cotton green shades rendered fast to washing byaftertreatment with with formaldehyde. The new dye is after being dried and pulverized in the shape of its sodium salt a dark powder easily soluble 1n water with a greenish coloration, soluble in concentrated sulfuric acid with a yellowish-black coloration. tion with stannous chlorid and hydrochloric acid para-phenylenediamin sulfonic acid, 1.4 diamino 2 naphtholethylether, metaamino'benzenyl 1.2 naphthylenediamin 6- amino-5-oxy-7-sulfonic acid and aminoresorcin. It has in a free state most probably the formula:

naphthylene-5-oxy-7-sulfonic acid of the salted out, pressed ofl, dissolved in water" Yielding upon reducand rediazoti'zed with 6.9 parts of sodium I V nitrite and 50. parts of hydrochloric acid, the d-iazo compound is then added to a solution containing 11 parts of resorcin in 500 parts of water and 40 parts of sodium carheated to 7 0-C. and the dyestutf 1s- .bonate, then salted out. It yields on cotton brilliant green shades which are rendered fast to washing by after-treatment with formaldehyde.

thylenediamin-fioxy l 3 Example 3: The product: 'oXalyl-para-' phenylenediamin 1.7 -'na.phthylamin "s'ulfonic acid-l-meta-amino-benzenyl-Lil-naph- ''-sulfonic acid is"produced according to Example 1. The dyestufl' is then mixed up with 100 parts ofwater and 150 'parts of caustic soda lye (30 per cent.) and boiled for half an hour. The.

caustic soda is neutralized with hydrochloric acid, the dyestuif 1S salted out and pressed. It is redissolved in water and tetra-zotized with 13.8 parts of sodium nitrite and 80 parts of hydrochloric acid.

I The mixture is stirred until the nitrous acid has disappeared. Then the tetrazo com-. pound is added to a solutioncontaining 22 parts of resorein in-500 parts ot water and 64 parts of sodium carbonate which is heated to 70 C. The dyestuff is salted out with common salt, pressed off and dried. It yields on cotton green shades.

The process of Example 3 is carried out in the same way if instead of 2 molecules of compound, a meta ami iophenyl derivative of the 2-amino-5-naphthol-7-sulfonic acid.

and a benzene derivative dyeing cotton in green shades which are rendered fast to washing by after treatment with formicv aldehyde, substantially as described.

2. The new, polyazodyes being derived from a meta-aminobenzenyl derivative of the 2 amino 5 naphthol 7 7 sulfonic acid which are after being dried and pulverized in the shape of their alkaline salts dark Y powders soluble in Water yielding upon reduction with stannous chlorid and hydrochloric acld an aromatic ammo compound,

a diamino compound, a meta-aminobenzenyl derivative of the 2-amino-5-naphtho1-7-s1ilfonic acid and a benzene derivative dyeing" cotton in green shades which are rendered fast to Washing by aftertrea'tment with formic aldehyde, substantially as described.

3. The new polyazo dyes being derived from a meta-aminobenzenyl derivative of the 2 amino 5? naphthol -'7 sulfonic acid which are after being dried and pulverized in {the shape of their alkaline salts dark powders solublein water: yielding upon reduction with stannous chlorid .and hydrochloric acid an aromatic diamin, another dlanuno compound, a meta-aminobenzenyl derivative of the 2-amino-fimaphthol-7-sulfonlc acid and a benzene derivative: dyeing cotton in green shades which are rendered fastto-washlng by aitertreatment \Vlll] formic aldehyde, substantially as described.

4. The new polyazo dyes being derived from a meta;aminobenzenyl derivative of the 2 amino 5 naphthol 7 s sulionie acid which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water; yielding upon -reduction with stannous chlorid and. hydrochloric acid a para-phenylenediamin, another diamino compound, a meta-aminobenzenyl derivative of the 2-aniino-fi-naphthol- 7-sulfonic acid and a benzene derivative' 7 dyeing cotton in green shades which are rendered fast to washing by after treatment with formic aldehyde, substantially as described.

5. The new polyazo dyes being derived from a meta-aminobenz'enyl derivative of the 2-amino-5-naphthol-7-sulfouic acid which are after being dried and pulverized in the shape of'their alkaline salts dark powders soluble in water; yielding upon reduction with stannous chlorid and hydrochloric aeid para-phenylenediamin sulfonic acid, another diamino "compound. anietaaminobenzenyl derivative of the EZ-amino-finaphthol-7-sulfonic arid and a benzene derivative; dyeing cotton in green shades which are rendered fast to washing by aftertreatm'ent with formic aldehyde, substantially as described.

6. The newpolyazo dyes being derived from a meta a'minobenzenyl derivative of v the 2 amino 5 naphthol 7 sultonic acid which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble 1n water; yielding upon reduction with stannouschlorid and hydro-' chloric acid an aromatic amino compound, a diamino derivative of naphthalene, a metaaminobenzenyl derivative of the 2amino-'3- naphthol-7-sulfonic acid and a benzene derivative; dyeing cotton in green shades which are rendered fast to washing by aftertreatment with formic aldehyde, substantially as described.

7. The new polyazo dyes being derived from a'meta-aminobenzenyl derivative of the 2-amino-5-naphthol-7 -sulfonic acid which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in Water; yielding upon re acid a para-plienylenediamin, a diamino dein the shape of their alkaline salts dark powders soluble in water; yielding upon reduction with stannous chlorid and h'ydrochlorlc rivative of naphthalene, a meta-aminobenzenyl derivative of the 2-am1no-5-naphthol- 7-sulfon1c acid and a benzene derivative;

which is after being dried and pulverized in the shape of its sodium salt a dark powder easily soluble in water with a greenish coloration; soluble in concentrated sulfuric acid with a yellowish-black coloration; yielding upon reduction with stannous chlorid. and hydrochloric acidpara-phenylenedialnin sulfonic acid, 1.4 diamino 2- naphthol ethylether, meta alninobenzenyl- 1.2 naphth ylenediamin-(S-amino-5-oxy-7-s1ilfonic acid and aminoresorcin; dyeing cotton green shades, which are rendered fast to dyeing cotton in green shades which are rendered fast to washing by aftertreatment with formic aldehyde, substantially as described. I 9. The new polyazo dyes being derived from a meta-aminobenzenyl derivative of the 2 amino 5 naphthol 7 sulfonic acid which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water; yielding upon reduction with stannous chlorid and hydrochloric acid a para-phenylenediamin, a diamino derivative of naphthalene, a meta-amin'obenzenyl derivative of the 2-a1nino-Smaphthol- 7-sulfonic acid and amino resorcin; dyeing cotton in green shades which are rendered fast to washing by aftertreatment with formic aldehyde, substantially as described.

10. The new azodye which has in a'free state most probably the fermula:

set our hands in the presence of two subscribing witnesses.

AUGUST BLANK. CARL 1-1 EIDENREIOH. JOHANNES JANSEN.

Witnesses Lows VANDORY, HAUR BRi'IoKNER. 

